SA115360577B1 - A process for production of oligomer product from hydrocarbon feed stock - Google Patents

Abstract

The present invention relates to a process for production of oligomer products from olefinic C4 feed stocks comprising isobutene, butenes, butanes, butadienes and mixture thereof. Particularly, the present invention relates to a process for the preparation of oligomers using olefinic C4 feed stock in presence of tertiary butyl alcohol (TBA) and iso propyl alcohol (IPA). Fig. 1

Description

1 Process for producing an oligomer product from hydrocarbon feedstock

A process for production of oligomer product from hydrocarbon feed stock Full description Background of the invention A process for production of oligomer products containing four carbon atoms comprising isobutene olefinic feed stocks feed; butadiene compounds; butane compounds; Biotin isobutene compounds and a mixture of the above. specially; The present invention relates to a process for preparing butadienes oligomers using a four-carbon olefin feedstock in the presence of iso propyl (IPA) and tertiary butyl alcohol (TBA) as an alcohol into an oligomer. A well known light olefins process is a well known light olefins conversion process that uses different catalytic systems to produce several desired end products. The process of converting iso-0-butene to an oligomer is specifically the process of converting iso-butene 150501606 to a dimer. high octane gasoline Important for the production of high octane gasoline blending ingredient 007 The conversion of isobutene to a dimer is a well known side reaction in the production process

Ja and exothermic (MTBE) Methyl Tertiary Butyl ether Permanent excess with respect to scaling ratio methanol J stil is large. to avoid dimer formation; 1 is kept by reducing the molar ratio of methanol to isobutene. The quantitative MTBE needed to produce the [F/118/A] dimer can be produced in the same reactor. A similar type of process to produce Vo VEOTE EP No. 1181/a mixture of secondary butyl alcohol [1181/a] secondary butyl alcohol uses the addition of premethanol in different molar ratios along with a filtered feedstock containing on four carbon Yo atoms containing isobutene to the reactor that uses the catalyst for the oligomerization process.

_ Ad —_

With more alcohols and ethers added as a new feedstock the cost of producing a product will increase

dimer and this will affect the process costs when applied in the industrial field.

In an oligomerization reaction using ion exchange resin as a catalyst specifically in

The process of converting isobutene to a dimer to isooctene; Different polar compounds are used

© as a selective enhancer of the dimer product. Tertiary butyl alcohol (TBA) is a

These polar components which are widely used in the dimerization process as a booster

selective.

TBA is one of the more expensive chemicals to be produced commercially through a process

Well known Oxiran as described in US Patent No. FYOVIYO Some Patents 0 such as US Patent No. 80797755; International Application No. 17 YYEEY has made efforts

To extract alcohol in particular TBA using energy and cost efficient processes

such as extraction; double distillation and others. Since TBA cannot be easily extracted

To form a stable boiling solution with water.

The in situ production of TBA in a dimerization reactor as disclosed in US Patent 1 ($V 0a YY IS No. 628774 +/ 00101) will develop both the reaction competitiveness and

Obtaining unwanted product selectivity (Led) for TBA and dimer. As both interactions

They require a different reaction environment, which cannot be provided in a single reactor.

US Patent No. 00007/00076149 describes a process for the selective conversion of isobutene to

Oligomer to di-isobutene in the presence of TBA as a modifier to improve selectivity. Yo The mentioned modifier is prepared in a separate Jolie and the free modifier is separated to an extent

large amount of water and sent to the oligomerization reactor where isobutene reacts in the presence of

Said modified material that has been separated to selectively form di-isobutene. is not given

A clear description of the method for separating the substance (Alara) in this application.

Abbreviations and definitions

— ¢ — ¢ Tertiary butyl alcohol 35 — TBA ¢ Isopropyl Alcohol IPA “Tri Methyl Pentene—1 TMP-1 - 4 ¢Tri Methyl Pentene-2 Y— Trimethylpentene «VEE - Y-TMP

Methyl Tertiary Butyl ether 5 (butyl ju) Methyl - MTBE ©

Fluid Catalytic Cracking — FCC

Research Octane Number Laboratory Octane Number - RON In the context of the present invention; A dimer means a product from the process of converting a feedstock containing four atoms into an oligomer; restricted to the dimerization process; iso-olefin carbon of isoolefin 0 primarily comprising iso-ooctane 150001606 » a combination of oY in 1-1100 and 7 4 ; 11/5-?, also known as di-isobutylene ©01-15051017160. The dimer also includes a product of a co-dimerization reaction i.e. a reaction between isobutene and n=butene 50161765 as 0« dimethyl hexene » 7© dimethyl 1-hexene-3 dimethyl ga 4 1 + 6 methyl-? dimethyl-2-hexene and others. VO means primer produced from the process of converting a four-carbon isoolefin feedstock into an oligomer; Restricted to a trimerization process comprising primarily triisobutylene present as cf oY oY 2 7-pentamethyl heptene 1- and 7 4 7 >-pentamethylheptene-7. similarly to dimers; Trimers also exist in different isomer forms BT Ted oF oY Jie Methylheptene -? and others. 0 GENERAL DESCRIPTION OF THE INVENTION The present invention relates to a process for producing oligomer products from four-carbon olefin feedstocks comprising isobutene; biotin compounds; butane compounds »

Co Butadiene compounds and a mixture of the above. specially; The present invention relates to a process for preparing oligomers using a four-carbon olefin feedstock in the presence of butyl (IPA) and isopropyl alcohol (TBA) tertiary alcohol. The present invention also relates to a process for the continuous and stable production of a mixture of alcohols from carbon ae ores having hydrocarbons with olefinic feeding; Which includes hydrocarbons 0 in the range of 012-603. in a favorable aspect; The feedstock comprises propylene 007 isobutene and a mixture of the above. The same time in the reaction zone of the secondary butyl alcohol the secondary alcohol the reaction environment to produce water free alcohols with maximum selectivity Eliminate gag where 0 and accordingly make the process auspicious (AY) Alcohols & TBA needed To the external addition of the entire catalyst in the hydration reaction zone is kept in wet form; with the same lil and alcohols IPA to the maximum TBA always to increase selectivity wetting the level of hydration Alcohols are produced at a continuous rate Stabilized by Ua butyl secondary alcohol. Jie Other hydration reaction zone Maintain continuous hydration of the catalyst in hydration reaction zone 1 and other alcohols in a separate zone of IPA grade hydration reactors (TBA) as they are produced Greater reaction control to produce alcohols as required in the oligomerization range; an additional step of extraction of excess alcohols is eliminated in the final current observed; This saves the process and other alcohols produced in the IPA; TBA reaction zone on costs. As it is directed to the region of the conversion reaction into an oligomer; The need for pale daly) 0 and related problems are also resolved in the present invention. The primary advantage of the invention for heating TBA and other alcohols produced in the hydration reaction zone is free of IPA TBA is that it is water and requires no separation step to extract the anhydrous alcohols. Furthermore it; Various alcohols and ethers from an external source are not required to improve the selectivity of the dimer product in the daly of the present invention. Methanol added in the prior art documents mentioned shall be consumed immediately Yo

By reaction with isobutene to form MTBE which leads to a continuous accumulation of 1/185 in the combined product and requires its removal at least as a purge stream; Which in turn makes the Und section complex in shape. In the jal aspect of the present invention” the IPA (TBA) and other alcohols produced are directed in a separate hydration reaction region (J) Wika the oligomerization reaction region connected serially to the Jeli hydration region. The hydration process is carried out at a spatial velocity of the olefin in the range of 01 (AY-01 h); temperature in the range of 0 - 01 Tr degrees Asie pressure in the range of 11 to ye The process of converting the four-carbon isobutene feedstock into a 0-oligomer is performed by reacting the four-carbon isobutene feedstock with a mixture comprising tertiary butyl alcohol and isopropyl alcohol in a zone The oligomerization reaction in the presence of the catalyst to obtain the dimers varied The molar ratio [PAL] in a mixture of 0/8A and 188 varies from 01 to 79 00. The oligomerization process is performed at a spatial velocity of the olefin In the range from 1 to 101 hours -1; temperature in VO range from 6 - 010 degrees gfe pressure in the range from 4 to 11 bar. Obtained by process Ey of the present invention for mixing with a vat of gasoline comprising a reforming product JE in the range 75-7595 by weight” an isomerization product in the range 1-775 by weight; F gasoline CC gasoline in the range of “-01 4 7 7 by weight and naphtha 1800178 in the range of 0 - 70 by weight to form 0 compound gasoline to improve the octane number number ©00180. The amount of dimer used to prepare a gasoline compound is in the range from 1.9 to 77 by weight of the gasoline compound. Furthermore it; The present invention provides a process for producing trimers by feeding the first portion of a four-carbon feedstock comprising isobutene; propylene and water to

—y— the hydration reaction zone to produce the product comprising tert-butyl alcohol and isopropyl alcohol; and feeding the second part of the four-carbon feedstock comprising isobutene to the oligomerization reaction zone. feeding a portion of the product obtained after rehydration to the oligomerization reaction zone; conversion of the four-carbon feedstock to produce a four-carbon catalyst comprising isobutene to an oligomer in the presence of the oo catalyst cascade comprising dimers; Fragmentation of the effluent stream into portions comprising dimers from said fraction comprising 1607/6/08 8 portion and recirculation of the split dimers to the hydration reaction zone; For the product comprising tertiary butyl alcohol; isopropyl alcohol; Alcohols containing eight carbon atoms and unconverted dimers. Feeding part of the product obtained after recycling to the conversion reaction zone to 0 trimers Oligomers to obtain trimers Brief explanation of the drawings A process for producing products from The oligomer is an olefin feedstock that, in form: 1, contains four carbon atoms, where; The four-carbon feedstock channeled to (©) 8 (Y) as one of the components is split into two embryos (1) comprising an isobutene Vo hydration reaction region (7) and a reaction region Conversion into an oligomer (9), respectively. The percentage of the reaction ranges in the reaction zone Lad in the propylene feed (Lo A) to 1.090 in the feed (7) (9) from to 770 by weight to Feedstock containing four 1 with a ratio of (1) reaction zone of metals Ja carbon atoms (7). Water (0) can be added preferably _ water or any water for example; condensate Steam to the poisons zone water free of 08185 00 hydration of the corresponding olefins (1) hydration reaction zone Water is added in an amount less than or equal to the capacity of the catalyst to hold the respective olefins. Always at the same wetting rate of the catalyst. Specifically Je lal) The humidity in the limiting area should be in the range of 750- 72950 from 3938 The catalyst retains moisture This in turn helps to maintain a constant yield of alcohols p Lee Madar .moisture holding Yeo

—A— Hydration reaction in the hydration reaction region (6); Accordingly, the ratio of alcohols to isobutene is maintained at the entrance to the oligomerization reaction zone (5). The product from the reaction zone together with isopropyl (V) enters the stream (A) 5 (7) into two streams Ua (7) alcohol; butyl tertiary alcohol and undenatured propylene and butylene compounds Which is produced to from (01) which fuses with the product (A) the oligomerization reaction region (). Enter_stream © which is a fractionation column to separate the products. 11 The reactor is separated ( 4) to the region on lighter components having a boiling point (VF) the products into two of the different pieces; the stream has a boiling point. YO stream has a true boiling point greater than (16) the Augie stream has a Real YO less than Unconverted propylene is partially converted from reaction region (1) to the corresponding dimer product in (2) reaction region 0

Saal) How much water is added so that; Equal to or less than the ability of the catalyst to hold moisture. The essential of the invention is that it does not require any separation step for the extraction of the anhydrous alcohol. Also, alcohols are produced at a constant rate by maintaining continuous hydration of the catalyst in the reaction zone. The catalyst is kept in a continuous state of hydration. Many side reactions are excluded. Lay hydration. In the hydration reaction zone. A portion of the synthesized alcohol mixture is directed from the 0 hydration reaction region to the oligomerization reaction region as the selectivity modifier. The synthesized alcohol mixture (4) increases the selectivity of the dimer product in the oligomerization reaction zone; plug flow reactor Jie batch reactor any type of conventional reactor can be used ¢ continuous stirred bed reactor tank reactor “bubble columnreactor” fluidized bed reactor fluidized bed reactor 0 etc. in both reaction zones. Figure ?: A process for producing oligomer products from olefinic feedstocks is described. Which contains four carbon atoms where the feedstock containing four carbon atoms which as one of the components is divided into two embryos (7) 8 (©) and directed to (1) containing isobutene reaction zone The hydration (7) and the oligomerization reaction zone (4) respectively

Feed to (1) 5 (3) From 00 to oo, A only the propylene feed (£) enters the reaction zone (7) in a ratio of 1 to 7780 by weight to the four-carbon feedstock AY) Water (0) preferably Water DM or any water free of metals and toxins eg steam condensate may be added to the reaction zone (1) for hydration of the corresponding olefins. © Water is added in an amount less than or equal to The ability of the catalyst to retain moisture present in the reaction zone to maintain the same hydration rate a of the catalyst This in turn helps maintain a constant yield of alcohols over the course of the hydration reaction in the hydration reaction zone (1); the product is partitioned from the hydration reaction zone (1) ) also to two of the streams (A) (V) and stream (7) along with isopropyl alcohol; tertiary butyl alcohol and the unconverted propylene and butylene compounds produced 0 enter the oligomerization reaction region (3) The product from the oligomerization reaction region (2) Wad is split into two streams (01) and (11); (01) lal which merges with stream (A) and enters into the region (VY) which is a hash column to separate products. Products are separated into two different lots; Stream (VY) includes lighter components that have a true boiling point of less than YO °C; The stream (VE) Vo has a true boiling point greater than YO degree Age The purge stream (11) produced from reaction region (3) is recycled back to reaction region (1) reaction The advantage of the invention is that it increases the conversion of olefins by increasing the temperature introduced to the hydration reaction region and beneficially also forms a heavier alcohol which in turn increases the selectivity of the 0-trimer product in the oligomerization reaction region ( 9) The trimer product can be used as a fuel additive, in the production of new acids, etc. The amount of recycled product is in the range from 75-7979 by weight of the total new feed and the molar ratio of isobutene to isooctene (dimer) At the entrance to the oligomerization range is in the range from 1:1 to .0:* the yield of alcohols with eight YO carbon atoms is in the range from 1.59 to 77.5 by weight. The unconverted dimer of a reaction region

-1- Rehydration to the oligomerization domain where it reacts with a four-carbon feedstock that includes isobutene and produces a trimer. The increased yield of three- and four-carbon alcohols and the formation of eight-carbon alcohols in the hydration zone favors the production of trimers in the oligomerization range. A process for producing oligomeric products from olefin feedstocks is described. iY is a © shape containing four carbon atoms where; The four-carbon feedstock which as one of the components is divided into two parts (7) 8 (©) and directed to (1) comprising isobutene the hydration reaction region (1) and the oligomerization reaction region (9) Respectively, the proportion of propylene feed input (£) only in the reaction zone of A feed to (1) and (9) ranges from 09 to 09 by weight to the feedstock containing four carbon atoms 7700 to 1 Hydration (7) with a ratio of 0 otherwise any water free of minerals and toxins DM Water (0) can be preferably added water (7) eg steam condensate to the hydration reaction zone (1) For the hydration of the corresponding olefins. Water is added in an amount less than or equal to the ability of the catalyst to hold the moisture present in the reaction zone to always maintain the same hydration ratio of the catalyst. This in turn helps to maintain the hydration reaction yield in the reaction zone (1). The product of Jae constant region of alcohols at 0 together with iso sa (7) daa (A) current (7) reaction (1) is further divided into two streams propyl alcohol; tertiary butyl alcohol and propylene The unconverted and butylene compounds produced (3) to the reaction region which is 11 the reaction region (9) to the region (01) which fuses with a product (A) entering the current is a column Segmentation to separate products. The products are separated into two different lots; 00 degree centigrade; YO shall be on lighter components having a true boiling point less than (VF) current included

Aggie true boiling point YO over dap (VE) of the stream is recycled back into the hydration reaction region (VE) of the stream (V0) purge stream is taken (9). To produce heavier alcohols and to inhibit the formation of heavier oligomers (tetramers) in the reaction zone (7)

-11- The new feed (Mea) the amount of the recycled product is in the range from 75-779 by weight from, and the molar ratio of isobutene to isooctane (dimer) is at the entrance of the conversion range to be the yield of alcohols containing An eight atom .0:* to 1:1 oligomer in the range from 77.5 to 77.5 by weight. The unconverted dimer of the 1,9-carbon reaction region enters a range from hydration to the oligomerization zone where it reacts with the four-carbon © feedstock containing isobutene and produces a trimer. The increased yield of three- and four-carbon alcohols and the formation of eight-carbon alcohols in the hydration zone favors the production of trimers in the oligomerization range. A process for producing oligomeric products from olefin feedstocks is described. tf form containing four carbon atoms where; The four-carbon feedstock having 0 as one of the constituents is divided into two parts (7) 8 (©) and directed to (1) comprising isobutene hydration reaction region (1) and conversion reaction region Oligomer (9), respectively.The percentage of propylene feed input (£) only in the reaction zone of A feed to (1) and (9) ranges from 09 to 7780 by weight to the feedstock containing four carbon atoms. 1 Rehydration (1) with a ratio of DM otherwise any water free of minerals and toxins DM Water (0) can be added preferably water (1) Vo eg; vapor condensate to the reaction zone (1). ) to hydrate the corresponding olefins. Water is added in an amount less than or equal to the ability of the catalyst to hold the moisture present in the hydration reaction zone to always maintain the same hydration ratio of the catalyst. This in turn helps to maintain a constant yield of alcohols over the course of the reaction Rehydration in the reaction zone (76); the product is divided from along with Gas (V) and the stream (A) 5 (7) also enters the reaction zone (1) into two streams 0 isopropyl alcohol Tertiary butyl alcohol and ber and unconverted butylene and butylene compounds that are (3) produced to the oligomerization reaction region (4) to (01) which fuses with the (A) product Jay current which is A segmentation column to separate products. The products are separated into three (VY) zone Yo on lighter constituents having a real boiling point less than (VF) l of the different lots; YO includes the same

_— \ \ _ seclusion degree. The current (VE) has a true boiling point in excess of 110°C. The current (Vo) has a real boiling point in the range from YO °C to 110 °C. The purge stream (VT) is taken from the stream (V0) which is a concentrated dimer product comprising >7297 pure dimer product (sale) and cycled back to the hydration reaction region (1) to produce 0 alcohols which It contains eight carbon atoms, which also suppresses the formation of heavier oligomers (tetramers) in the reaction zone (3) The amount of recycled product is in the range from 75-7979 by weight of the total new feed, and the molar ratio of isobutene to isooctane (dimer) is at the entrance The oligomerization range is in the range from 1:1 to .0:*© The yield of alcohols with 8 carbon atoms is in the range from 1.59 to 77.5 by weight. Unconverted from the hydration reaction zone to the oligomerization zone where it reacts with the four-carbon feedstock containing isobutene and produces a trimer Increased yield of alcohols with three and four carbons favors the formation of alcohols with eight carbon in the hydration region (produce all) in the oligomer conversion range. Vo Fig. 0: shows the effect on product yield due to change in catalyst hydration over time. Figure 1: Shows the effect of mixing an oligomer product in a vat of gasoline on Research Octane Number (RON). from isobutene; Using an acidic catalyst including an ion exchange resin catalyst in several four-carbon olefin feedstock reaction systems comprising isobutene »butane compounds »butane compounds »butadiene compounds and a mixture of the above. specially; The present invention discloses a process for preparing oligomers

— \ — Using a four-carbon olefin feedstock in the presence of tertiary butyl alcohol (TBA) and isopropyl alcohol (IPA) the present invention Wad discloses a process for the continuous and stable production of a mixture of alcohols from olefinic feedstocks Which include hydrocarbons with a number of carbon atoms in the range from C12-C3. 5 In a favorable aspect, the feedstock includes propylene iso Od ga and a mixture of the above. According to the present invention; The light olefinic hydrocarbon feedstock comes into contact with acidic catalysts that include catalysts of lon exchange resin in two different reaction zones; which are connected in the form of a parallel sequence and operate under different conditions, in particular to favor the production of IPA (TBA) other alcohols such as secondary butyl alcohol and heavier alcohols (C8+) in the first reaction zone and the oligomerization process In the second reaction zone, the feed to the process is a four-carbon feed stream that includes isobutene as one of the components available from any of the refinery units such as Naphtha cracker Yo unit (FCC lal cracker). Delayed Coker, isobutane dehydrogenation etc. In addition to the above, Lal also includes Propylene as a feedstock with a minimum purity of 7700 wt. From any of the processes such as (FCC) delayed coking unit; cracking of naphtha and propane dehydrogenation and others. The feedstock containing 0 with four carbon atoms also includes 0-butane len «isobutane Biotin, butenes; 0?butadiene, and others. The propylene feedstock Lad contains propane and propadiene. Two different catalysts are used in the hydration reactor and oligomerization reactor respectively. The catalyst used in the rehydration reactor has a minimum wetting holding capacity of 50 to

— ¢ \ — by weight of the catalyst. The catalyst is a polymer based cation exchange 6517 resin having a concentration of acid sites less than 0 eq/kg; more specifically Suni less than ; eq/kg and a surface area less than [Ya 5 0 g and an average pore diameter of less than YOu angstrom.© The catalyst used in the oligomerization reactor is a polymer based cation-exchange resin with a concentration of acid sites greater than Æeq/kg and a surface area greater than 560 [Ya g and an average pore diameter of more than You an angstrom and having a minimum expected benzene content ranging from 770 wt. with the four-carbon feedstock comprising isobutene to the oligomerization reaction zone; feeding the product comprising tert-butyl alcohol and isopropyl alcohol to the oligomerization reaction zone; and converting the four-carbon feedstock comprising the iso Butene to oligomer NO in the presence of the catalyst to produce dimers in one of the atmospheres b Ey of the present invention; The product comprising tert-butyl alcohol and isopropyl alcohol is obtained by the process comprising: A feeding propylene four-carbon feedstock comprising isoCO su and water to the hydration reaction zone; and Ye b. Carry out a hydration process for the four-carbon propylene feedstock in the presence of the hydration catalyst to obtain the product comprising tert-butyl alcohol and isopropyl alcohol. OEY

AG \ _ in another aspect also Gy of the present invention; The product comprising tert-butyl alcohol and isopropyl alcohol is obtained simultaneously in said hydration reaction zone and a portion of the product comprising tert-butyl alcohol and isopropyl alcohol is transferred to the oligomerization reaction zone. 0 in another aspect also Gy of the present invention; The dimer yield is obtained in a range of

JO by weight with a dimer selectivity of more than 0/797 sides according to the present invention; A process for the continuous and stable production of a mixture of HAT in one: alcohols”; The process includes a. feeding olefin feedstock and water to the hydration reaction zone; and ho to carry out a hydration of the olefin feedstock in the presence of the catalyst in the dale reaction zone) where the wetting rate constant of the catalyst reaches 7460 of its moisture holding capacity; To obtain a stable yield of alcohol mixture. In another aspect as well according to the present invention; The olefin feedstock comprises hydrocarbons having a number of carbon atoms in the range C12-C3 Vo in another aspect Ey Wal of the present invention; The olefinic feedstock is selected from the four-carbon feedstock that includes isobutene; propylene or a combination of the above. on the jal side also the Ey of the present invention; The four-carbon feedstock includes isobutene; biotin compounds; butane compounds; Butadiene compounds and a mixture of the above. On the AT side of the present invention; The propylene feedstock also contains propane. 0 in another aspect also according to the present invention” propylene ranges from 1 to 7780 by weight from the ore

_a \ _ in the af side also according to the present invention; The wetting ratio of the catalyst is maintained in the hydration reaction zone in the range of = 746 from the moisture holding capacity of the catalyst. In another aspect also Ey of the present invention; Water is added in the hydration reaction zone in the range of 1 to 219 wt. of feed. © In another aspect also according to the present invention; The product obtained in the hydration reaction zone comprises tertiary butyl alcohol; isopropyl alcohol; secondary butyl alcohol and alcohols on the Al side; The present invention provides a process for producing trimers; The process comprises: (a) feeding the first portion of the four-carbon feedstock comprising iso(0)butene”propylene and water to the hydration reaction zone to produce the product comprising tert-butyl alcohol and isopropyl alcohol; (b) feeding the second portion of the four-carbon feedstock comprising isobutene to the oligomerization reaction region; (c) feeding a portion of the product obtained in step (a) to the conversion reaction region 1 to oligomer; conversion of the four-carbon feedstock comprising isobutene to an oligomer in the presence of the catalyst to produce the dimer-comprising effluent; (d) Fragmentation of the flowing stream into segments containing dimers; (e) Recirculation of a split from said fraction containing the dimers to the hydration reaction zone; For the product containing tertiary butyl alcohol; Isopropyl (Jal) alcohols of 0 | 8 carbon atoms and unconverted dimers; (f) feeding a portion of the product obtained in step (e) to the oligomerization reaction region to obtain the trimers.

for \ _ in a preferred aspect [FER of the present invention; The amount of dimer that is recycled in step (e) in the Ale pall production is in the range of 75-7759 wt of the new feed. In another favorable aspect the fraction containing dimers obtained in step (d) comprises >2560 dimers. In a favorable Gy Al aspect of the present invention; The catalyst used in the © hydration reaction area is a polymer based cation exchange resin having a concentration of acid sites less than 5 eq/kg » surface area less than 4 m Al g and an average pore diameter less than µ ang. On the other hand, the catalyst used in the oligomerization reaction zone is a polymer based cation exchange resin having a concentration of acid sites greater than 0 eq/kg; surface area greater than 0 © m a / g; The average pore diameter is in excess of ¼ ang and the content of DE0 phenylbenzene ranges from 00 to 785 wt. In terms of Gy Und AT of the present invention; The present invention provides a combined gasoline formulation comprising: to .5/7297 by weight of the oligomer product obtained by the process according to the present invention; and 705-755 a tub of gasoline comprising heavy reformat product in the range of VO in the range of FCC by weight; Gasoline 775-01 wt. isomerization product in the range from 700 wt. and naphtha in the range from zero wt. 240 by leakage in a preferred aspect; The combined gasoline composition according to the present invention has an octane rating

YA = #0 ranges from 0 in another aspect of the present invention; The ratio of a four-carbon feed stream to the hydration reaction region and the oligomerization reaction region ranges from 0.00 to cA in another aspect of the present invention; The current flowing from the oligomerization reaction region is split into two segments; Lighter components have a real boiling point less than YO °C and an Adda boiling point greater than YO °C.

m \ _ in the AT side of the present invention; The current flowing from the oligomerization reaction region is fragmented into three different segments; lighter components having a true boiling point below Yo °C; A component having a real boiling point in the range YO °C to 10 °C and a component having a real boiling point greater than 101 °Aue Gy© of the present invention; The ratio of the first part of a feed stream containing four carbon atoms to the part

The second is from a feed stream containing four carbon atoms ranging from 09 to A, and the propylene feed is in a ratio ranging from 1 to 7700 by weight from the first part of a feed stream containing four carbon atoms. The water used in the hydration reaction is cre WIA Metals and toxins laa, 0 of invention Jal Water is added in the hydration reaction zone aie less than or equal to the catalyst's ability to

A moisture retention. Ey is based on the rate-constant hydration of the catalyst in the range of −4 from the ability of the catalyst to retain moisture to obtain a constant yield of alcohols in the first reaction zone (hydration zone). The product/alcohols obtained in the hydration reaction zone comprise isopropyl alcohol; butyl alcohol; Heavier alcohols (+08), undenatured propylene and butylene compounds.

Vo At the end of describing the essential aspects of the present invention; The following non-exhaustive examples illustrate a specific model of it. EXAMPLE 1 Variation in product yield due to change in catalyst hydration over time 01 g of Hydration Catalyst is immersed in water in the range of 700

Yo from the catalyst's ability to hold moisture and load it into a tubular reactor; The feed comprising 7980 wt isobutene and 1072 wt propylene is passed through the reactor at 10 °C and a pressure of 11 bar. The products are separated from the reactor and analyzed for detailed hydrocarbon analysis every two hours. It was found from Figure 0 that over time the yield of tertiary butyl alcohol and isopropyl alcohol decreased, while the yield of the dimer product and product increased

q —_ \ _ the terminator. This clearly shows that the water in the catalyst reacts with propylene and isobutene in the feed to form isopropyl and tertiary butyl alcohol and while the water is being consumed; i.e. decrease in wetting of the catalyst over time; The dimer formation is dominated by isooctene and the trimer. It should be noted that no water is added after the catalyst is loaded through any means into the reactor. © Ung finds that 0.75 wt. of the water in the catalyst is consumed within an hour of the process and the remaining 70 eo by weight of water is consumed over the Jae the remaining three hours of the process.It is thus evident that catalyst hydration needs to be maintained precisely the percentage of continuous and constant production of alcohols over time; without excess water in the reactor Flowing Stream Current Y Jie Ye Effect of Wetting the Catalyst on the TBA Yield It is clear from Example-1 that the selectivity and yield of the required products depends on the amount of water present in the catalyst therefore it is required to discover the effect of wetting of the catalyst on the TBA yield only; For proof of concept, a moving tank batch reactor is used for this purpose and from a 0 g ge VO catalyst is loaded in each experiment with 0 75 wt. of wetting”; 7970 wt. YY g of Isobutene shipped in each batch along with 1-hexane as a diluent 0 Then the reaction is carried out at 11 bar pressure and at 15 °C 0. Nitrogen is used as an inert gas for the compression process. The specified reaction time is 15 minutes. The results are presented in a table as shown below: Table 11: REE a 7 “ENON] TY, VY] 8: TBA yield (from water + isobutene) ‘

vy.

CT

From the above table it is clear that with the increase in catalyst wetting ratio 7; The selectivity of 19/8 increases while the iso-butene conversion decreases. Although Gaal iso-conversion decreases it is noted that with the increasing amount of water content in the case increases leading to a higher total yield of TBA-butene; Selectivity is relative to

TBA ee of wetting in the product. 7900 waterproof in excess of ET is found more specifically in JA therefore it is required to maintain a wetting of the catalyst less than or equal to

A :-76 range from Example? in a continuous pattern TBA Effect of catalyst wetting on the yield of 0 which supports 7980 percent of catalyst wetting in a continuous pattern; TBA is loaded to form a yield and selective 1-hour tubular and the spatial velocity of the olefin is kept at Jolie required amount of catalyst in bar and 15°C respectively. VT pressure and temperature are kept at 1 The effect of the percentage of water content on the total nutrition was studied, and the results are explained below: Table ?: Vo same

_— \ \ _ grit z 5 = | > It is evident from the above table that an increase in water content increases TBA yield and decreases product yield

from the oligomer. TBA yield nearly matches results up to 7980 by weight of hydration Gy

For an example? Thus, the recharge lasts for 510 hours of operation under cycle number ? to check what

If the TBA is continuous and stable. It is noted that even after 1501 hours of operation; be toll

TBA© is stable and there is no decrease or improvement; It is described in cycle no. ;. It is also noted that

There is no water in the product; This shows that anhydrous alcohol containing TBA can be produced with yield

stable and without any separation step by maintaining a balanced proportion of catalyst hydration on the face

selection. The injected water is consumed after reaching 798 percent of catalyst wetting

fully continuous production of TBA and other alcohols and thereupon avoided slipping into conversion range 0 to oligomer:

example;

Effect of temperature on alcohol yield during recycling of an oligomer product

To discover the effect of the increase in the isobutene conversion yield and TBA yield, the temperature was increased from

5 to YO °C by feeding pure preheated feed of Iso-octane at VO high temperature to maintain the temperature input to the hydration reaction zone at VO Lise

It was found that there was an increase in the outcome from 751.17 by weight to 770.59 by weight. That explains that

An increase in temperature in the range from 5 to VO will increase the conversion as well

TBA score

Table:

_— \ \ _ 3 7 = | > Yield 1 M-isooctane by weight Vay 0 Yield Trimethyl Pentanol “ 7 wt No 5 It is clear from the above example that the recirculation of the oligomer product purge stream is either from the lower portion of the oligomerization band or from the lower portion of the fractionation column or from the middle part of the fractionation media will increase the shall degree introduced into the rehydration reactor (since the temperatures of the recycle streams are higher than the temperature of the new feed stream) thus increasing the yield of 0 alcohols. It is also observed that heavier alcohols (alcohol with eight carbon atoms) are formed during the recycling process in the hydration reaction region. EXAMPLE-0: Effect of the mole ratio of methanol to isobutene on the selectivity of MTBE and isooctene This example shows that if methanol and isobutene are treated in an oligomer reactor by changing the molar ratio of methanol to isobutene, isooctane and MTBE can be produced in the same time 0 using the same oligomerization catalyst. The reaction was performed in the containing systems

Ad —_ \ _ tubular reactor at HLA and at 0 hr-1 spatial velocity for isobutene. The results obtained are illustrated below: Table: Session | Selective ratio | selectivity molar number average YA selective aa) 54 Yet «Y li deli | degree | Transform MTBE | Selective to ISO | heat | iso | Based on |71/0- | TMP | isobutene ad | Biotin |Isobutene Y VI Octane' BE | B It is noted from the above table that when the molar ratio of methanol to isobutene is reduced from 017 to 0.7, the selectivity increases relative to isobutene and it is clear that there is both Methyl Tert Butyl Ether (MTBE) ) and isooctane jointly (Lovie) the same methanol is used

_— ¢ \ _ as an ingredient (dad) Therefore with the use of methanol the yield and selectivity of isooctane cannot be increased due to the reaction of methanol with isobutene to form MTBE. Example 6 Effect of selectivity and yield of isooctane when only TBA is used as an additive © is The feed that is used in the following experiments has a composition as shown in the following table: Table ‎to The composition containing four carbon atoms (7 by weight) trans-? Trans—2-Butene Cis-7-butene Cis—2- Butene 01 g of dried oligomerization catalyst was loaded into a tubular reactor; Systems with the Jolie include a gas feed module and a liquid feed module so that a liquid C3/C4 feed 0 is injected into the reactor in a precisely controlled manner via high-pressure pumps; In addition two liquid additives can be pumped into the reactor. After the reactor, a two-stage separation system allows the gas to be separated into liquid form. In the first stage heavier and in-phase liquid products can be separated

Table 1: 7 (Agi) lighter liquid products can be separated ally and recycled back to the systems by weight of TBA velocity a velocity al lee spatial heat yield | Nutrition that | 7 default |iso (actual); for iso | contain | Convert | selective | oS is the “pressure degree cycle”; | Butene four atoms iso-iso B41-number 1|homeostasis| 1 hour bar | carbon butene | octane | Basis 1 | | ا ْ َ | a a | 1 º B 1 | º 1 | | | ' Experiments in the above system were carried out in a tubular reactor in a continuous mode of operation. © tertiary butyl alcohol is only used as an additive in different operating conditions as mentioned in the table above. An increase in the degree of reaction sha and a decrease in the spatial velocity leads to an unwanted reaction and accordingly a decrease (a Wn) and the yield of isooctane 3. It is clearly noted that it cannot be increased

_a\_ selectivity and maximum yield of isooctane to over ,IVA 4 and 75 by weight respectively while only /18 is used as an additive for the dimerization process. Example VY Combined effect of isopropyl alcohol and TBA on iso-octane selectivity and yield o Table tv IPA + TBA Total feed velocity Total total spatial heat containing A Selectivity | toll (actual); Limzo | on four atoms | Convert |ISO S| Cycle Pressure Degree; OgS| (Ot M Isooctane Jbl Biothem| A H-1 | wt Biotin | 7 # wt BEE A mixture of isopropyl alcohol and tertiary butyl alcohol produced in the rehydration reactor is passed through the systems containing a tubular reactor under various operating conditions It is noted that in a mixture of isopropyl alcohol and tertiary butyl alcohol the selectivity of isooctane increased to more than AA Gals know that it is not possible to increase the selectivity of isooctane without abandoning the conversion Biotin Bhai 13d 0 Low conversion of isobutene; lower total isooctane yield even in selective Ala

high. Nevertheless; In the present invention; Surprisingly, it is observed that the combined use of isopropyl alcohol and tertiary butyl alcohol in the oligomerization reactor greatly increases both the yield and the selectivity of the dimer product; When compared to the yield and selectivity when only tertiary butyl alcohol was used (example = T) for a fixed outcome test, each experiment was repeated at an interval of © YE hr in a continuous running mode. It is noted that the observed stable outcome and selectivity were obtained in both cases. Example A Effect of mixing an oligomer product in a basin of gasoline The product is mixed as is obtained in Example-7 which includes an oligomer product having more than 7960 dimer selectivity in different ratios in a basic basin of gasoline comprising 75 by weight of heavy reformatting product » 775.7 by weight of 060 gasoline and 77075 by weight of isomerization product to obtain a composite gasoline formulation with improved properties in terms of laboratory octane number (RON) as described in JSS It is clearly seen from the figure that with the increase in the mixing ratio of an oligomer product ranging from 0.4 to 2.2 yo 2 by weight, the RON of synthesized gasoline increases from 90.4 to 54.7 4. The example represents The above mentioned is one of the uses of an oligomer product as a fuel component; although it can also be used in various products a others such as alkylphenols; surfactants and others. The essential features of the present invention are as follows 0 The principal sd of the present invention are the production of alcohols, an oligomer product and the flexibility of maintaining product selectivity Gy for needs which in turn depends on cost. The gal advantage of the invention is that the alcohol required to maintain the selectivity of the dimer/trimer product is produced in-house using the same feedstock used for the oligomerization process.

A —_ \ _ Another advantage of the process is that it does not require any separation step to extract the anhydrous alcohol. Lay Alcohols are produced at a constant rate by maintaining continuous hydration of the catalyst in the hydration reaction zone. While the catalyst is kept in a continuous state of hydration; Several side reactions are excluded in the hydration reaction region. © Another advantage of the invention Jal is the production of a mixture of alcohols at a constant rate in the hydration reaction region which increases both the selectivity and yield of the dimer product in the oligomerization range to over ATE A respectively. Jian Another advantage of the present invention is that recycling an oligomer product from the bottom of the reactor to the inlet of the hydration zone increases the input temperature to the feed hydration zone which Ye also increases the yield of alcohols in the hydration zone. Another advantage of the invention is that recycling an oligomer product in particular iso-octane in the hydration zone forms trimethylpentanol in the range of 0.5 - 77.5 wt; It is an alcohol containing eight carbon atoms. Other sie is also related to the present invention in the recycling of the dimer product in the hydration zone which V0 in turn enters into the oligomer conversion range where it increases the selectivity and yield of the primer product. same

Claims (1)

—vq- protection elements; The process includes oligomerization into an iso-olefin oligomer A process for the conversion of an iso-olefin-1 containing: A four-carbon containing isobutene feedstock (a) Feedstock “oligomerization to a conversion reaction zone” to isobutene oligomer and isopropyl alcohol tertiary butyl alcohol (b) feeding product comprising tertiary butyl alcohol © and « oligomerization to the iso propyl alcohol oligomerization reaction zone (c) crude conversion Feed containing four carbon atoms that includes isobutene dimers; in the presence of a catalyst for the production of oligomerization into an isobutene tertiary butyl alcohol oligomer, whereby the product that includes butyl alcohol is obtained, comprising: le by iso propyl alcohol and isopropyl alcohol 0 ; four-carbon feedstock feeding propylene (1); water to the hydration reaction zone; isobutene comprising isobutene; propylene for four-carbon feedstock daly Carrying out a (Y) tertiary process in the presence of a hydration catalyst to obtain the product comprising iso propyl alcohol and isopropyl alcohol 01 and 90% of its capacity to 71 where the percentage wetting ranges Process per claim 0 whereby the product comprising butyl-" is obtained in the same iso propyl alcohol and tertiary butyl alcohol Ye time in said hydration reaction zone and a portion of the product comprising butyl alcohol is transferred to the iso propyl alcohol and tertiary butyl alcohol reaction zone ,. oligomerization The conversion to an oligomer =” since – F is the process Gy of the dis protection) a dimer yield is obtained in the range of 967/750 by weight with a selectivity of the dimer up to > 0 765. ;- a process to produce continuous and constant for a mixture of alcohols; The process includes: © ( ) feeding an olefin feedstock and water to the hydration reaction zone; (b) perform hydration of the olefin feedstock in the presence of the catalyst in the hydration reaction zone; The hydration rate constant for the catalyst ranges from Ve to 9640 of its moisture-holding capacity; To obtain a stable yield of alcohol mixture. Ys # - process pursuant to claim of where the olefinic feedstock comprises hydrocarbons with C in the range C3-C12 - process pursuant to claim ©; Where the olefinic feedstock is selected from the Lal ore containing four carbon atoms, which includes isobutene; Vo propylene ; or a combination of the above. —V process Ga, for either numerical claim Tg) where the four-carbon feedstock includes isobutene ; butenes biotin compounds; butanes; Butadienes and a mixture of the above. 70 A = the two-claim process ge) where the propylene feedstock also contains propane .propane 4- the process pursuant to claim 1; where propylene ranges from 1 to %Y by weight Yo . of the feedstock containing four carbon atoms. yy and ;; wherein the water is added in the range of 1 process according to any of the two protections numerical -0 to 9019 by weight of the feed. 14 of and ;; Where the product obtained 1 includes the process pursuant to either of the two numeric claims -1; tertiary butyl alcohol is found in the hydration reaction zone on tertiary butyl alcohol and secondary butyl alcohol © iso propyl alcohol is another four-carbon alcohol. 2005; The process includes: trimers Process for producing trimers 1- (a) feeding a first portion of the four-carbon feedstock comprising an iso-ine and water to the hydration reaction zone in the presence of propylene; propylene isobutene Ve and iso tertiary butyl alcohol hydration to produce product comprising tertiary butyl alcohol; It involves the iso « oligomerization to the biotin isobutene oligomerization reaction region (c) feeding a portion of the product obtained in step 0 to the VO conversion reaction region and converting the four-carbon feedstock which oligomerization to an oligomer in the presence of the catalyst to produce oligomerization to an isobutene oligomer comprising isobutene; dimers a stream containing dimers; (d) fractionation of the stream into a fraction containing dimers To the region of interaction of the dimers (e) Recycle a moiety of said fraction comprising the dimers Ye « tertiary butyl alcohol hydration; For the product that contains butyl alcohol tertiary carbon atoms old ; alcohols containing 150 propyl alcohol undenatured isopropyl alcohol; and dimers and dimers (f) feeding a portion of the product obtained in step (e) into the conversion reaction region where the hydration ranges trimers to obtain oligomerization into a Yo oligomer — \ As the percentage of the hydration catalyst is constant between 71 and 90 96 of its moisture retention capacity. -0 Process [FCP for claim VY where the amount of dimer being recycled in step (e)© is in the range of 75-7079 wt of new feed. 6- The Gay process of the claim OY, where the part includes dimers obtained in step (d) containing > 906960 dimers. -1#Y Operation under any of Claims 1 ; 5 VY where the catalyst used in the hydration reaction zone is a polymer-based cation exchange resin 16517 having a concentration of acid sites less than 0 eq/kg; A surface area of less than [Yo tr g] and an average pore diameter of less than YOu angstroms. -1 “Vo process Wy for any of the protection elements) 5 VY where the catalyst used in the hydration reaction zone is a 16517 resin resulting from a polymer-based cation exchange with a concentration of acid sites greater than about © eq/kg; Surface area more than 56 [Yo] gm, average pore diameter more than You angstrom, divinyl benzene content from Yo to 96 d by weight. 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B Po i Yo 1 i i H H : H A 1 0 i 1 : i 1 1 1 1 1 " 1 a a | 4 A — 1 sms Yi i 1 / i A a an + Saha b 0 Ad 7 — — “toll of wandering 36 zin Bhd JAG of pilgrims a z om ate uo | b l , EE e b oF ; Brave ' 0 0" 8“ \ Fry e! 0 1 | | penrk: eel = | 03 \ .ba \ 'frase for ei: AS oEvY SS CL = 0 z 8 . 7 Z « RON Marjej \ \ : 0 ERE a a a a a a a a EE EERE a a a The validity period of this patent is twenty years from the date of filing the application, provided that the annual financial fee is paid for the patent and that it is not invalid or forfeited for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties, and industrial designs, or its executive regulations issued by King Abdulaziz City for Science and Technology; Saudi Patent Office P.O. Box TAT Riyadh 57??11 ¢ Kingdom of Saudi Arabia Email: Patents @kacst.edu.sa